Dyeing



Patented Apr. 26, 1938 UNITED STATES PATENT OFFICE DYEING Hamid Blackshaw, Richard Walter Hardacre,

and Wilfred Archibald Sexton, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application March 8, 1935, Serial No. 10,122. In Great Britain March 8, 1934 10 Claims.

A. The present invention relates to improveof cellulose acetate, wool, and other alkali sensitive fibers with azo dyes.

C. An object of the invention is to dye alkali sensitive fibers of either animal or vegetable origin with an azo dyestufi without subjecting the fiber to the degrading influence of a caustic alkali. Another object of the invention is to dye materials with ice colors in a bath free from caustic alkalis. v

D. The objects of the invention are accomplished, generally speaking, by treating an alkali sensitive animal or vegetable fiber, or a material derived therefrom, with an amino-arylamide of 2:3-hydroxy-naphthoic acid containing a solubilizing group (sulfo, carboxy, or thioglycollic acid groups) in the aminoaryl radical in the presence of a mild base and in the absence of a caustic alkali, and developing the color by treatment with a solution of a diazo compound or with a nitrous acid solution. Among the materials to which the process can be applied are wool, cellulose esters, regenerated cellulose. The basic substance may be either organic or inorganic.

E. Exemplary oi. the very large number 01 primary arylamines which may be used as the diazo components in this invention are the following: 4-nitro-2-amino-anisole; 2 fi-dichlor-aniline; 4- chloro-2-amino-toluene; 2-methoxy-1-naphthylamine; 2-methoxy-aniline; 2-phenoxy-aniline; 2-ethoxy-aniline; 2-chlor-5-methyl-aniline; 2- methyl-aniline; 2-methoxy-5-methyl-aniline; 2- methoxy-4-ch1or-5-methyLaniline; 2 -dimethoxy-aniline; 2: 5-diethoxy-aniline; 2: 5-dimethoxy-4-chlor-aniline; 5-brom-2-methoxy-aniline; 3-iodo-6-methoxy-aniline; line; 3 -methyl-4-chlor-aniline; oxy-aniline; 3-chlor-6-ethoxy-aniline; -3-ethoxyaniline; 3-phenoxy-aniline; 3-methoxy-aniline; 3 brom G-phenoxy-aniline; 3-iodo-6-phenoxyaniline; 3-brom-6-methyl-aniline; 3-chlor-6- methyl-aniline 3 methyl aniline; 3-brom-5- methylaniline; 3-chlor-fi-phenoxy-aniline; 2 5- dimethyl-4 chlor aniline; 4-ethyl-aniline; 4- amino-benzotrifiuoride; 4-chlor-2-methoxy-aniline; 4-brom-2-methoxy-aniline; 4-brom-2-ethoxy-aniline; 4-iodo-2-methoxy-aniline; 4-methoxy-aniline; 4-chlor-2-ethoxy-aniline; 4-phenoxy-aniline; 4-ethoxy-aniline; 4-brom-2-phenoxy-aniline; 4-methoxy-2-chlor-aniline; 4-chlor- 2-methyl-aniline brom-3-methyl-aniline;

3-iodo-6ethoxy-ani- 3-brom-6-eth,

line; 4-methyl-aniline; 4,-chlor-2-phenoxy-aniline; 4-methoxy-3-chlor-aniline; 4-phencxy-2- chlor-aniline; 4-ch1or-2:5-diethoxy-aniline; 3- chIor-Z-methyl-aniline; 3-chlor-2-methoxy-aniline; alph'a-naphthylamine; beta-naphthylamine; ortho-chlor-aniline; meta-chlor-aniline; meta nitraniline; 4 chloro-2-nitraniline; 4- chloro-2-amino-anisole; 5-nitro-2-amino-anisole; Lamina-4 benzoylamino 2 5-diethoxy-benzene; N-(para-amino-benzoyl) -aniline; dianisidine; alpha-amino-anthraquinone 3 amino carbazole; 2-nitro-4-methyl-benzene-azo-cresidine; 4 :4'-di amino-diphenylamine.

F. On wool a full shade having good iastness to milling is obtained notwithstanding that there is no caustic alkali in the padding bath. This is highly advantageous; with 2:3-hydroxynaphthoic arylamides which are void or solubilizing groups production of full shades can only be affected by the use of caustic alkali in the padding bath.

G. On natural silk similarly good results are obtained, the shades when sodium carbonate is used in the padding bath being even fuller than when caustic alkali is used. The affinity of the arylamide is good and the resulting dyeings are of fair fastness to degumming.

H. On cotton the aflinity is good and the shades produced are fast to soaping. The fastness to chlorine is also good.

I. The following examples illustrate the invention, without limiting it.

EXAMPLE I Cotton dyeing 2 parts of 2z3-hydroxynaphthoic-4-a.mino- 3-sulfoanilide are pasted with 9 parts of Turkey-red oil and 100 parts of boiling water are added. The mixture is heated, 10 parts of soda ash being added, and boiled until clear. The

clear brown solution is then made up with water.

to 1000 parts.

Cotton is steeped in the solution (20 parts solution to 1 part of cotton) for V hour at 25-30 0.; squeezed and then developed in a diazo bath in the way usual in the ice-color process. After the customary finishing treatment by soaping the following shades are obtained:

Diazo compound from Shade obtained 2:5-dichloroaniline Yellowish scarlet. x-Chlnroaniline- Do. o-Nitroaniline. Bright orange brown. 3-nitro-p-t0luidine Brick red. 4-chloro-2-nitroamlm Do. 5-nitro-o-tolu1d1ne. Do. fi-nitro-o-anisidine. Do. 5chloro-o-toluidine Bluish red 4-chloro-o-toluidine Dull red. 4-chloro-o-anisidine. Bluish red Dianisidine Blue black 4-benzoylamino2:5-dlethoxy Navy blue.

lllxmmII Dyeing or printing animal fibers especially wool and natural silk The printed fabric is dried, washed in water and finally soaped at 60 C. A bright red shade is produced.

b. 2 3-hydroxynaphthoic-4'-amino-3'-sulfoanilide may also be suitably brought into solution by pasting 1.5 parts with a little water and 0.3 part sulionated alkylated petroleum (British specification No. 274,611), adding 75 parts of boiling water then 4 parts of soda ash. The clear solution thus obtained is made up to 1000 parts with water.

Wool (1 part in 20 parts of solution) is steeped in the above solution for hour at 50 C., squeezed and rinsed with water and then developed in a. diazo bath. Diazotized 5-chloro-orthotoluidine gives a brick red shade.

c. 5 parts of wool are treated in a bath containing 5% of 2:3-hydroxynaphthoic-4'-amino- 3'-sulfoanilide (on the weight of cloth) .the bath being prepared as inflows:

0.25 part of product is pasted with 0.7 part of commercial triethanolamine and 150 parts of water are added. The wool is immersed into the warm liquor, which is gradually heated to boiling during the course of 2040 minutes. After boiling for 10 minutes 0.5 part of salt is added and a second similar addition is made after a further 10 minutes boiling. Boiling is continued for 30-40 minutes in all.

The wool is rinsed in water and then immersed in a cold bath of a diazotized amine containing approximately 0.25 part of amine per 100. After hour, the shade is fully developed and the dyed wool is rinsed and soaped for 2-3 minutes at 40. Diazotized fi-chloro-ortho-toluidine gives a red shade.

d. The 5 parts of wool which has been padded as in above is immersed for hour in 100 parts of water containing 0.25 part of sodium nitrite and 0.25 part of formic acid. Finally itis shade.

treated for 10 minutes in a cold 0.05% aqueous solution of sodium carbonate. After rinsing and ,soaping, the wool is dyed in a brownish-claret 0n silk the shade is claret.

Exmru HI Application to cellulose acetate ing 0.5 part sodium nitrite and 0.5 part of formic acid in 250 parts of cold water. After hour the material is treated for 10 minutes in cold 0.02% aqueous sodium carbonate and finally soaped at 60". A bright crimson shade possessing very good fastness to soap and free from marking off is produced.

Ii instead of 2:3-hydroxynaphtholc-4'-amino- 3'-sulfoanilide there is used the 3'-amino-4'-su1- foanilide, the shade produced is a bright red. A similar shade is produced'by the compound which is described in U. S. application, .Serial No.

EXAMPLE IV Application to union materials Wool-cotton union materials are dyed in solid shades by applying the products in the manner I described in Example II. Application of the compound is commenced at or near the boil with to the specific embodiments thereof except as defined in the appended claims.

We claim: 1. The method of dyeing wool which comprises mixing 2 3-hydroxynaphthoic-4'-amino-3 -sulfoanilide with triethanolamine and diluting with water, impregnating wool with the said solution and coupling with the salt from diazotized chloro-ortho-toluidine and naphthalene-1:5-disulionic acid. 1

2. The method of dyeing which comprises impregnating a textile material with an aminoarylamide oi 2:3-hydroxynaphthoic acid containing one of the group consisting of COOH and SOaH in lactam-forming position in the aminoaryl radical, and coupling it with a diazotized primary arylamine in the presence of a mild alkali.

3. The method of dyeing which comprises impregnating a fibrous material with an aminoarylamide of 2:3-hydroxynaphthoic acid containing in the aminoaryl radical a group from the class consisting of COOH and SOsH, and coupling it in the presence of a. mild alkali and in the absence of caustic alkali to a diazotiz'ed primary andamine. v

4. A textile fiber dyed with a compound formed by the coupling of a diazotized arylamine with 2:3 hydroxynaphthoic i'-amipo-3'-sulfoanilide in the presence 0'1. 9. mild alkali.

5. A textile fiber dyed with a compound formed by the coupling in the presence of a. mild alkali ot a diazotized arylamine with an aminoarylamide of'2z3-hydroxynaphthoic acid containing a lactam-forming', water-solubllizing group ad- Jacent to the amino group.

6. Textile fibers dyed with the dyestuff resulting from the coupling in the presence of a mild alkali of 2 3-hydroxynaphthoic-4"-amino-3'-sulfoanilide with diazotized 2:5-dichloro-aniline.

'7. Textile fibers dyed with the dyestuif resulting from the coupling in the presence of a mild alkali of 2:3-hydroxynaphthoic-4'-amino-3-sulfoanilide with diazotized B-nitro-para-toluidine.

8. Textile fibers. dyed with the dyestuff resulting from the coupling in the presence of a mild alkali of 2 :3-hydroxynaphthoic-4-amino-3-sulfoanilide with diazotized 5-nitro-ortho-anisidine. a compound represented in the form of its free 9. Material of the class described dyed with the 7 acid by the formula compound represented in the form of its free acid my1 N=N by the formula: v

5 Aryl-N=N I X 0B I o 0HN g g N H1 O in which X is a lactam-forming radical in lactam- 10 10 l forming position in respect to the NHz group.

)Q HAROLD BLACKSHAW. 0 0 RICHARD WALTER HARDACRE. 10. Material of the class described dyed with WILFRED ARCHIBALD SEXTON.

Certificate of Correction Patent No. 2,115,136. April 26, 1938.

HAROLD BLAGKSHAW, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 3, first column, lines 5-14, claim 9, in the formula, for the last nucleus and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 12th day of July, A. D. 1938.

[slim] HENRY VAN ARSDALE,

Acting Commissioner of Patents.

foanilide with diazotized 5-nitro-ortho-anisidine. a compound represented in the form of its free 9. Material of the class described dyed with the 7 acid by the formula compound represented in the form of its free acid my1 N=N by the formula: v

5 Aryl-N=N I X 0B I o 0HN g g N H1 O in which X is a lactam-forming radical in lactam- 10 10 l forming position in respect to the NHz group.

)Q HAROLD BLACKSHAW. 0 0 RICHARD WALTER HARDACRE. 10. Material of the class described dyed with WILFRED ARCHIBALD SEXTON.

Certificate of Correction Patent No. 2,115,136. April 26, 1938.

HAROLD BLAGKSHAW, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 3, first column, lines 5-14, claim 9, in the formula, for the last nucleus and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 12th day of July, A. D. 1938.

[slim] HENRY VAN ARSDALE,

Acting Commissioner of Patents. 

